Negative resist composition

Abstract

A negative resist composition is provided which is less likely to swell in an alkali developing solution. An alkali-developable negative resist composition is disclosed comprising a compound (A) which generates an acid upon exposure to radiation, and a resin component (B) which becomes insoluble in alkali under the action of an acid, wherein the component (B) is a resin component containing: (b1) a unit which becomes insoluble in an alkali solution as a result of the formation of a lactone under the action of an acid generated from the component (A), and (b2) a unit having an alcoholic hydroxyl group.

1. An alkali-developable negative resist composition comprising a compound (A) which generates an acid upon exposure to radiation, and a resin component (B) which is made insoluble in alkali under the action of an acid, wherein the component (B) is a resin component containing:
 (b 1) a unit which becomes insoluble in an alkali solution as a result of the formation of a lactone under the action of an acid generated from the component (A), and  
 (b2) a unit having an alcoholic hydroxyl group.  
 
     
     
       2. The negative resist composition according to  claim 1 , wherein the lactone is δ-lactone. 
     
     
       3. The negative resist composition according to  claim 2 , wherein the unit (b1) is a unit derived from a (meth)acrylate ester having δ-hydroxy acid bonded to a non-aromatic polycyclic hydrocarbon group. 
     
     
       4. The negative resist composition according to  claim 3 , wherein the non-aromatic polycyclic hydrocarbon group is a group in which two hydrogen atoms are eliminated from a non-substituted or methyl-substituted tricycloalkane. 
     
     
       5. The negative resist composition according to  claim 4 , wherein the unit (b1) is a unit represented by the following general formula (I): 
                 
 
       wherein R represents a hydrogen atom or a lower alkyl group. 
     
     
       6. The negative resist composition according to  claim 1 , wherein the unit (b2) is (i) a unit derived from an α-hydroxyalkyl acrylate ester. 
     
     
       7. The negative resist composition according to  claim 6 , wherein the unit (b2) is a unit represented by the following general formula (II): 
                 
 
       wherein R 1  represents a lower alkyl group, a non-aromatic polycyclic alkyl group, a hydroxyl group-containing non-aromatic polycyclic alkyl group or a lactone-containing non-aromatic polycyclic alkyl group, and n represents an integer of 5 or less. 
     
     
       8. The negative resist composition according to  claim 7 , wherein R 1  is a lower alkyl group. 
     
     
       9. The negative resist composition according to  claim 8 , wherein R 1  is a methyl group. 
     
     
       10. The negative resist composition according to  claim 7 , wherein n is 1. 
     
     
       11. The negative resist composition according to  claim 1 , wherein the unit (b2) is a unit derived from a hydroxyl group-containing non-aromatic polycyclic alkyl ester of (meth)acrylic acid. 
     
     
       12. The negative resist composition according to  claim 11 , wherein the hydroxyl group-containing non-aromatic polycyclic alkyl group, which constitutes the hydroxyl group-containing non-aromatic polycyclic alkyl ester, is an adamanthyl group having at least one hydroxyl group. 
     
     
       13. The negative resist composition according to  claim 12 , wherein the unit (b2) is a unit represented by the following general formula (III): 
                 
 
       wherein R represents a hydrogen atom or a lower alkyl group, and m represents an integer of 1 to 3. 
     
     
       14. The negative resist composition according to  claim 13 , wherein one hydroxyl group exists and the hydroxyl group is bonded to the adamanthyl group at the 3-position in the general formula (III). 
     
     
       15. The negative resist composition according to  claim 14 , wherein R is a hydrogen atom in the general formula (III). 
     
     
       16. The negative resist composition according to  claim 14  for the development with an alkali developing solution having an alkali concentration of 1.0% by mass or more. 
     
     
       17. The negative resist composition according to  claim 1 , wherein the component (B) is a copolymer containing the unit (b1) and the unit (b2) in a molar ratio of 1:9to9:1. 
     
     
       18. The negative resist composition according to  claim 11 , wherein the component (B) is a copolymer containing the unit (b1) and the unit (b2) in a molar ratio of 1:9 to 9:1. 
     
     
       19. The negative resist composition according to  claim 14 , wherein the component (B) is a copolymer containing the unit (b1) and the unit (b2) in a molar ratio of 8:2 to 4:6. 
     
     
       20. The negative resist composition according to  claim 19 , wherein the component (B) is a copolymer containing the unit (b1) and the unit (b2) in a molar ratio of 7:3 to 5:5. 
     
     
       21. The negative resist composition according to  claim 1 , further comprising a solvent (C), the solvent (C) containing water. 
     
     
       22. The negative resist composition according to  claim 11 , further comprising a solvent (C), the solvent (C) containing water. 
     
     
       23. The negative resist composition according to  claim 21 , wherein the solvent (C) contains propylene glycol monomethyl ether and water. 
     
     
       24. The negative resist composition according to  claim 1 , wherein the molar ratio of the (b1) unit to the (b2) unit is within a range from 1:9 to 9:1. 
     
     
       25. The negative resist composition according to  claim 1 , wherein the molar ratio of the (b1) unit to the (b2) unit is within a range from 4:6 to 3:7. 
     
     
       26. The negative resist composition according to  claim 1 , wherein the total amount of the unit (b1) and the unit (b2) is 50 mol % or more based on the component (B). 
     
     
       27. The negative resist composition according to  claim 1 , wherein the total amount of the unit (b1) and the unit (b2) is 70 mol % or more based on the component (B).